KR20060034334A - Antibacterial dispersed dyes having silver-containing modified sulfonamides and a method of preparing the same and antibacterial fiber thereby - Google Patents

Abstract

The present invention relates to a silver-containing antimicrobial disperse dye including a chromophore having a nitro group prepared by binding a silver-containing modified sulfonamides to an intermediate of the dye as a powerful antimicrobial reactor and a method for preparing the same.

By using a silver-containing antimicrobial disperse dye compound containing a chromophore having a nitro group according to the present invention, dyeing a polyester woven or knitted fabric which is a hydrophobic fiber can produce an antimicrobial fiber product having persistent and strong antimicrobial properties.

Silver-containing antimicrobial disperse dyes, nitro groups, sulfonamides, antibacterial fibers, silver sulfadiazines.

Description

Antibacterial dispersed dyes having silver-containing modified sulfonamides and a method of preparing the same and antibacterial fiber thus

The present invention relates to a silver-containing antimicrobial dispersion dye containing a chromophore having a nitro group prepared by binding a silver-containing modified sulfonamides to an intermediate of the dye as a powerful antimicrobial reactor, and a method for preparing the silver-containing antimicrobial dispersion The present invention relates to an antimicrobial fiber having various colors and antimicrobial properties by dyeing a polyester fabric which is a hydrophobic fiber by using a dye.

In general, textile products used in clothing and bedding, etc. must go through a dyeing process for coloring the textile material in the desired color according to the consumer's various tastes.

However, various fiber products manufactured as described above are inhabited by microorganisms due to poor storage, or by contact with the human body as a nutrient source of the secretions of the human body, the microorganisms inhabit and multiply, threatening the health of the human body, or causing odors in the products, Discoloration and withdrawal may occur, which may be a major factor in degrading product quality, such as durability and color fastness.

For this reason, textile products may be a carrier or a habitat for pathogen invasion. If they give antimicrobial properties to textile products, they can prevent the growth and proliferation of microorganisms, preventing infectious diseases, preventing odors, and preventing fiber contamination and embrittlement. You will be able to get a textile product.

Usually, antibacterial and deodorant processing methods are largely divided into post-treatment processing methods and yarn improvement methods. In the post-treatment processing method, the dye component is extracted from natural substances such as tricotweed, which has antimicrobial properties, to give antimicrobial properties (Korean Patent Publication No. 2000-007593), and antimicrobial components such as organometallic compounds and organic substances are crosslinked with fibers. Heat-fixing method on the fiber surface with reactive resin, and adsorption-fixing method of antimicrobial material on the fiber surface. In the yarn improvement method, a method of mixing and spinning an inorganic antimicrobial agent between polymers in a manufacturing step of synthetic fiber and containing the inside of the fiber, and a method of undispersing the copper compound in the fiber during coagulation and regeneration of the regenerated fiber, and There is a method of synthesizing a polymer by making an organic copolymer component having antibacterial properties.

On the other hand, antibacterial and deodorant processing is not for the purpose of sterilization or treatment, but is a process for suppressing the growth and growth of bacteria and fungi on the fiber. shall. In this sense, organometallic compounds such as organometallic mercury compounds, organotin compounds, organocopper compounds, and organozinc compounds used in the post-treatment process have very good bactericidal properties. Now, it is used in Japan, the United States, etc., and most of them are not used in textile processing for garments, but are used in some fields such as carpets, wallpaper, and other industries that do not come into contact with human bodies. Moreover, these organometallic compounds have problems in adhesion to fibers and durability of laundry, and thus have a limit in enduring antimicrobial properties.

In addition, general organic antimicrobial materials are easier to process than inorganic ones, and have been widely used until now because they do not affect mechanical properties, transparency, color, etc., but as mentioned above, the antimicrobial effect is not sustained and in particular, heat resistance. Use is limited in that it is inferior. In addition, some organic antimicrobial substances cause problems such as skin irritation and tearing. In addition, dyes extracted from natural materials have the advantage of imparting antimicrobial properties from the dyeing stage, but due to seasonal limitations, the extraction of dyes is limited and the disadvantages of using the mordant salt method using another heavy metal to improve the fastness, which is a disadvantage of natural dyes. have.

Inorganic antimicrobial material is substituted with inorganic ion such as zeolite, silica, alumina and other metal ions with excellent antimicrobial properties such as copper and zinc, and has a three-dimensional skeletal structure with fine pores. . On the other hand, metals such as copper and zinc are one of the few metals with strong antibacterial activity and high safety, and have been proved to be harmless to human body. Inorganic type has high stability compared to conventional organic type antimicrobial material because it has high stability such as high heat resistance and does not cause volatilization and decomposition, etc., and the antibacterial effect of inorganic type antimicrobial material is expressed by active oxygen ion. It has outstanding advantages that are not seen in materials. However, metal ions such as copper and zinc may deteriorate the resin or cause yellowing, thereby significantly lowering the commodity value. In addition, the inorganic antimicrobial material is generally more than a few microns in average particle size and wide range of particle size distribution may be the cause of trimming when mixed with fine fibers.

Presently, in the form of a dye to have an antimicrobial function in the dyeing process is the Republic of Korea Patent Publication No. 2002-0057322 'red antibacterial dye'. In the present invention, the antibiotic is widely used as a matrix of dyes to prepare dyes, and not only undergoes additional processing steps, but also has an antibacterial deodorization function by simple dyeing. do. However, because of the water-soluble properties of the antibiotics used in the above, because it is water-soluble dyes made of reactive dyes limited to cotton (棉), which is actually a hydrophobic fiber that is an acid fiber that requires antimicrobial in many areas, such as furniture, Gapet. Car seats, interior fibers, etc. There is a limit that can not be applied.

In general, antimicrobial agents are water-soluble and hydrophilic, so it is possible to synthesize them in the form of reactive dyes or acid dyes applied to cotton or nylon having a hydrophilic group on the substrate itself, but polyester is a representative hydrophobic fiber. It is not possible to apply it in the form of a disperse dye applied to it. Therefore, in order to be made in the form of disperse dyes used for dyeing the hydrophobic fibers of the polyester woven fabric, it is necessary to introduce a hydrophobic group into the matrix of the dye to improve the hydrophobicity of the compound.                         

On the other hand, silver (Ag) is a metal that is beneficial to the human body is already known. In the herbal wood, if the body has silver, the five intestines are comfortable, the mind and body are stable, and the body is lightened. And it is said that it is effective in the prevention and treatment of gynecological diseases such as mental disorders and cold-heartedness such as sports. With the recent increase in health concerns, the necessity of functional fibers and fabrics such as antibacterial and deodorizing functions in clothing and the like has been highlighted.

The present invention has been proposed to solve the problems of the conventional antimicrobial material used as the dye as described above, an object of the present invention to provide an antimicrobial disperse dye using a silver-containing modified sulfase as a powerful antimicrobial reactor and a method for producing the same. will be.

In addition, in the present invention, an antimicrobial disperse dye may be synthesized by using a substance having a hydrophobic group nitro group (-NO ₂ ) introduced into silversulfadiazine, which is applicable as a dye and has excellent antibacterial effect, as a matrix of the dye. It is another object of the present invention to produce a textile product having excellent durability that does not require an additional antimicrobial processing process and does not dissolve the dye and the color of the knitted fabric does not discolor.

The present invention relates to a silver-containing antimicrobial disperse dye prepared by combining silver-containing modified sulfonamides with intermediates of the dye as a powerful antimicrobial reactor and a method for producing the same.

The present invention also relates to functional antimicrobial fibers dyed with the silver-containing antimicrobial disperse dyes.

Specifically, the present invention relates to a silver-containing antimicrobial disperse dye prepared by combining various compounds having a nitro group with a chromophore and a silver-containing modified sulfase, a preparation method thereof, and an antimicrobial fiber using the same.

Hereinafter, the configuration of the present invention will be described in more detail.

Commonly used antimicrobial agents include penicillin, sulfonamides, fluoroquinolones, tetracyclines, aminoglucosides, and the like. Among these, it is widely used and can be used as an intermediate of dyes such as tetracycline, sulfonamide, and quinolone.

In the present invention, sulfonamide-based antimicrobial agents, particularly silver-containing sulfonamide-based antimicrobial agents, which provide antimicrobial properties by inhibiting metabolic functions such as nucleic acid synthesis of enzymes in microorganisms, are used.

Sulfonamide drug, or sulfonamides, which have strong antimicrobial properties, is a type of antimicrobial agent having SO ₂ NH ₂ groups. Gram-positive cocci (streptococci, pneumococci, etc.), Gram-negative cocci (meningococci, gonococci, etc.), Gram-positive bacteria (Escherichia coli, shigellae) ) And the like, and various other bacterial growth inhibitors. Sulfonamides have a common molecular structure of sulfanylamide, and sulfapyridine, sulfadiazine, sulfamerazine, sulfapyrazine, sulfatiazole and silver sulfa are shown below. There are various types such as silversulfadiazine.

Sulphamine

Sulfapyridine

Sulfathiazole

Sulfadiazine

Sulfapyrazine

Sulfathithiazole

Silver Sulfadiaizine

In the present invention, dyes using silver sulfadiazine (monosilver-4-amino-N-pyrimidylbenzenesulfonamide) of the following general formula 1 are most easily synthesized as an intermediate of dyes and excellent in antibacterial effect. Synthesize.

(General Formula 1) Silver Sulfa Diazine

Silver sulfadiazine is a derivative of sulfadiazine and is effective against yeast as well as antimicrobial ability against many gram-positive and gram-negative microorganisms, and is used topically and externally for the prevention and treatment of second and third degree burn sepsis. Used as an anti-infective agent.

Silver ions (Ag ⁺ ) combine with enzymes that control the respiratory tracts of bacteria and fungi, incapacitating their function and killing them, and sterilizing Staphylococcus aureus, which is the cause of odors, to prevent odors. Silvery and silver ions (Ag ⁺ ) have insect repellent because they avoid them. In addition, since silver is the metal with the highest conductivity and conductivity, it is also excellent in electromagnetic shielding and antistatic effect. High far-infrared emissivity can reduce fatigue of human body. All of the above-mentioned antimicrobial agents can be used as intermediates of dyes, and in the present invention, a silver sulfadiazine-modified intermediate is combined with various compounds having a nitro group as a chromophore to synthesize an antimicrobial dye such as Chemical Formula 1 below. It was.

(R ₁ is -H or -NO ₂ and A means chromophore with nitro group.)

Preferably the chromophore having the nitro group is 2- (1,3-diamino-4-nitrobenzene) -4-chloro-6-amino triazine.                     

Hereinafter, a method for preparing an antimicrobial disperse dye using a modified silver-containing sulfa agent according to the present invention will be described in detail.

The silver-containing antimicrobial disperse dye including the chromophore having the nitro group of Chemical Formula 1 of the present invention may be synthesized by a manufacturing method consisting of the following three steps:

(a) Silver sulfadiazine was treated with acetic anhydride to block the terminal amine group, followed by nitric acid and sulfuric acid to nitrate the benzene, and alkali treatment to recover the blocked amine to prepare 2-nitro silver sulfadiazine. step;

(b) subjecting cyanuric chloride to the first dehydrochlorination reaction with the 2-nitro silversulfadiazine;

(c) performing a second dechlorination reaction while slowly adding a material having a nitro group to the solution in which the first dehydrochlorination reaction has been performed.

According to a preferred embodiment of the present invention, a silver-containing antimicrobial disperse dye including a chromophore having a nitro group represented by the following Chemical Formula 2 may be synthesized by the following three steps:

(a) Silver sulfadiazine (General Formula 1) was treated with acetic anhydride to block the terminal amine group, followed by nitric acid and sulfuric acid to nitrate the benzene, and alkali treatment to recover the blocked amine to recover 2-nitro silver sulfa. Preparing a diazine (formula 2);

(b) subjecting cyanuric chloride (formula 3) to the first dehydrochlorination reaction with the 2-nitro silversulfadiazine;

(c) performing secondary dehydrochlorination while slowly adding 1,3-diamino-4-nitrobenzene (general formula 4) to the solution in which the primary dehydrochlorination proceeds.

 (General Formula 1) Silver Sulfa Diazine

(General Formula 2) Nitro Silver Sulfa Diazine

(General Formula 3) Cyanuric Chloride

(Formula 4) 1,3-diamino-4-nitrobenzene

Features and other advantages of the present invention as described above will become more apparent from the description of the non-limiting examples described below. However, the following examples are merely illustrative as specific embodiments of the present invention and should not be understood as limiting the scope of the present invention.

Example: Preparation of Yellow Disperse Dye of Formula 2

After dispersing 53.6 parts of silver sulfadiazine (formula 1) in water at room temperature, 15.35 parts of acetic anhydride are added slowly to block the terminal amine. After blocking, 9.5 parts of nitric acid and 14.7 parts of sulfuric acid were slowly added to the reaction solution, followed by nitration reaction, and then 8.4 parts of KOH was slowly added to recover the blocked terminal amine, thereby preparing 2-nitro silver sulfadiazine (Formula 2).

The reaction mixture was cooled to 5 ° C. or lower, and then 27.7 parts of cyanuric chloride (General Formula 3) was dispersed in distilled water and acetone, cooled to 5 ° C. or lower, and then the dispersed solution was prepared in 2-nitro silver sulfadiazine (General Formula). 2) Proceed with the first dechlorination reaction while slowly adding to the solution.

23 parts of 1,3-diamino-4-nitrobenzene was added to a separate reaction container, dissolved in distilled water by adding a small amount of acid, and slowly added to the solution subjected to the first dehydrochlorination reaction. Proceed with dehydrochlorination.

After the reaction was completed, the pH was adjusted to 7, filtered with a filter paper, and dried in vacuo to give 60.9 parts of a yellow-based antimicrobial dispersion dye of Formula 2 below.

(Formula 2)

After adding glacial acetic acid and a dispersant to a 1.0% aqueous solution of the yellow-based antimicrobial disperse dye compound of Formula 2 obtained as described above, a salt solution is prepared, followed by dyeing at 130 ° C. for 60 minutes to prepare antimicrobial fibers by soaping and drying.

Antimicrobial Evaluation Test

By using the antimicrobial test method of the KSK 0693-2001 fabrics, the antimicrobial test was performed on the fabrics dyed at a concentration of 1% o.w.f.

Test Sample Bacteriostatic reduction (%) Strain Ⅱ Strain II Blank - - Yellow Antibacterial Dye (1% o.w.f) 99.9 99.4

Antimicrobial Test Conditions

The antimicrobial test conditions for the silver-containing antimicrobial disperse dyes of the present invention are as follows:

1.Test Method: KSK 0693-2001

2. Species: 1) Strain I: Staphylococcus aureus ATCC 6538

                    2) Strain II: Klebsiella pneumoniae ATCC 4352

3. Inoculation concentration: 1) Strain I-1.3 × 10 ⁵ / ml

2) Strain Ⅱ-1.5 × 10 ⁵ pcs / ml

As described above, dyeing a polyester woven or knitted fabric of a hydrophobic fiber by using a silver-containing antimicrobial disperse dye compound containing a chromophore having a nitro group according to the present invention produces an antimicrobial fiber product having continuous and strong antimicrobial properties. It can manufacture.

Claims (5)

Silver-containing antimicrobial disperse dye of Chemical Formula 1 including a chromophore having a nitro group. (Formula 1)

(R ₁ is -H or -NO ₂ and A means chromophore with nitro group.) The chromophore containing nitro group according to claim 1, wherein the chromophore having nitro group is 2- (1,3-diamino-4-nitrobenzene) -4-chloro-6-amino triazine. Containing antimicrobial disperse dyes. A method for preparing a silver-containing antimicrobial dispersion dye containing a chromophore having a nitro group according to claim 1, comprising the following three steps: (a) Silver sulfadiazine was treated with acetic anhydride to block the terminal amine group, followed by nitric acid and sulfuric acid to nitrate the benzene, and alkali treatment to recover the blocked amine to prepare 2-nitro silver sulfadiazine. step; (b) subjecting cyanuric chloride to the first dehydrochlorination reaction with the 2-nitro silversulfadiazine; (c) performing a second dechlorination reaction while slowly adding a material having a nitro group to the solution in which the first dehydrochlorination reaction has been performed. 4. The process for preparing silver-containing antimicrobial disperse dyes according to claim 3, wherein the nitro group-containing material is 1,3-diamino-4-nitrobenzene. An antimicrobial fiber dyed with a silver-containing antimicrobial disperse dye containing a chromophore having a nitro group according to claim 1.